Process for dyeing with dyestuffs insoluble in water or water-insoluble leuco compounds of dyestuffs.



, UNITED STATES PATENT oFFroE;

mrcnanr. rmmsxx, or UER INGEN oN-THE-RHINE, GERMANY, ASSIGNOR 'ro MESSRS.-

WEDEKIND :& (10., B. 1-1., OI UERDINGEN-ON-THE-RHINE, GERMANY.

. PROCESS FOR DYEING WITH DYESTUFFS III SOLUBLE III WATER ORYWATER-INSOLUBLE I No Drawing.

7 To all whom it mag concern:

Be it known that I,-,MIoHAE ILJINsKx, chemist, subject .of the Czar of Russia, -re-' siding at 1 Uerdingen-omthe-Rhine, Germany,;have1nventeda new and useful Process for Dyeing with Dyestufis Insoluble in Water or. ater-Insoluble Leuco" Compounds of Dyestuffs; and I do hereby declare the following-to be a full, clear, and exact description of the same,

Experimental investigations have led to the extremely surprising and technically i1n-' 'portant result that many dyeing compounds inso luble in Water, such as vat dye-st'ufls,

water-insoluble leuco-metal'salts of the vat dye-stuffs (leuco-salts of magnesium, zinc,

acid or alkaline aqueous suspension capa- 7 ble of acting readily even cold upon unmor dented or previously mordanted vegetable or animal fibrous materials and .in this way to form with'the-fiber a kind of lbose or unistable' compound which possesses, however,

sufficient stability to be thereafter in one- -way or another transformed into stable and ings can be obtained.

fast dyeings; It is very surprising that in The technical advantages of this method are manifold. Since the dye-baths can be kept very concentrated, large and therefore expensive dye-vats become unnecessary; the

costly extended boiling oflarge quantities of liquid' 'in mordant dyeing islikewise sup-' pressed, as 'well as the movement of the goods treated therein. Since; the absorption of the dye-stuffs, if certain conditlons areobserYed takes place so well as to be without residue, the vat dyer is able to carry out the dyeing with accurately measured quantities of dyestuff. The troublesome and time-wasting restoration of the vat to the desired content.- of dye-stuff be comes" unnecessary. In particular with mixed tints of two or more dye-stuffs which in le uco' form act upon thefibrous material, in the'vat with differing rapidity, the technical advantage of the method'becomes clear.

A-further advantage is due to the circumstance that the equalization of the dyestuffs Specification of Iietters Iatent.

LEUCO COMPOUNDS OF DYESTUFFS.

takes place upon the formation of the first unstable compound. The dyer is, therefore,

relieved of thetroubleof the equalization in carrying out the second part of the dyeing closed, mechanical apparatus. From' all these advantages there resu ble cheapening of the dyein The more concentrated the dye-baths are kept-,the quicker and more thorough isthe lts 1 a consideraabsorption of theadye-stuflf suspended in the bath.' The. greatest affinity forthe dyestuffs suspended in water is shown by silk fibers, wool fibers coming next. In the case of cotton, it is necessary to adhere to considerably more concentrated V dye-baths, if

is desired to obtain a thorough absprp tion of the dyestuff. If the bath is-too con centrated, the dyein s' turn-out slightly uneven. However, su cient equalization can be finally obtained by padding the goods in 7 the cold for a longer. time.

The formation of. the first unstable 'compounds of the dyestufi's with the fiber'takes place with vat dyestuffs in the same Way as t with mordant dyestuffs insoluble in water;

during the second process, the transformation of the unstable into the .stable dyeing proper, it is necessary to resort to various processes according to the nature of the dyestufi's. I i In the case of vat dye-stuffs, the unstabledyeing, which is sufliciently resistant to cold and warm water, but not to soap, may be successfully transformed into a fast dyeing by vatting the unstable compoundupon the fibrous material and then oxid zing it in the air. It is remarkable, that with the correct method ofworking no quantity of the dyestuffs Worth mentioning 15 in this way dissolved from the fiber. In the Ger-" man patent specification 17-7952 (class 8 there is described a process accordingv to; which the .dyestufi thickened- Wlth glue, rubber, etc.,-is spread upon the, cotton material,

.and the material so prepared is then treated 10o with an alkaline reducing solution. But

that process 1's only patented for indan Patented Sept. 26, 1916. I .Application filed December 10, 1912. Serial No. 735,930, i

throne dyestufis (it is expressly mentioned in the description that no useful results are obtained with indigo), whereasthe method of the present invention is capable of generalapplication; Further, the two methods. have nothing in common for the reason I The vetting upon the fiber isin all. cases carried out in sucha manner that after the ening or sulfur.

grams of indigo.

dyestufl' is completed in a fewminutes. The padding is continued a little longer, Wherethat it was not to'be foreseen that the unreduced vat dyestuffs would also be able-to act upon the fibers Without adhesives, in the insoluble form andfrom aqueous suspension,

. and that in spite of the absence of adhesive,

these, additions of dye-stuff.- are for the greater part not again dissolved by the alkaline reducing solution. In. the process of the present invention, the insoluble dyeing compounds are free from adhesives, thick- In the case of mordant dyestuffs insoluble in water, it is sufficient to steam or to heat under Water the water-resisting unstable dyestufi' compounds. The'niethods of working will be explained by the following examples:

A. VAT DYESTUFFS..

F first 0peratz' 0aUnstabZe combination of the dyestafi.

Example 1: 10 kilograms of cotton, dry or moistened, are padded at ordinary temperature in 40 liters of neutral or feebly-alkaline indigo suspensioh, containing 200 The absorption of the by the equalization is. very considerably promoted. 1

Example 2: 10 kilograms of cotton are padded as in Example 1 in 40 liters'of a neutral or feebly alkaline suspension containing 200 grams of algol-orange with 100 grams of algol-blue. Y

Example 3: '10 kilograms of cottonare.

padded as in Example 1 in 50 liters of a neutral or feebly, alkaline suspension containing 150 grams of indanthrene and 150-grams of thioindigo-red.

. Example 4: 10

' taining 300 grams of alg'ol orange. The ab- 1 sorption of the dyestufi' is completedv in a few minutes.

Second operation.

- absorption of the'dyestufi in the first operation the wrung out goods are placed in an kilograms of-wool, dry or: .moistened, are padded as in Example 1 with rangers alkaline hydrosulfite solution, which is preferably mixed with common salt or sul 'the case of indanthrene 'it will be much greater than with indigo or algol dyes. The total quantity of liquid'need' be only large enough to cover evenly the goods in an un pressed condition, 3 In the preferred manner of Working, which in any special case can easily be determined, the dyestufi may with success be reduced upon the' fiber in such a way, that no quantity Worth mentioning is dissolved from the fiber. After the reduction is completed, the goodsare wrung, hung. out, Wound and soaped.

B. DIORDANT DYESTUFFS.

First operatiorr-Formatipn 0f the unstable- Zrzise.

"Example 6: 10 kilograms of cotton mordanted with alumina as usual for Turkeyred ready for dyeing, are padded at ordinary temperature with 50 liters of a sus'- pension, containing 200 grams of alizarin with or Without addition of acetate of lime and. Turkey-red oil. The absorption :of the dyestuff iscompleted in a few minutes.

Example 7 10 kilograms of cotton moi-.- danted ior dyeing as usual. for Turkey-red, are padded as in Example 6 with 50 liters of a suspension containing 100 grams of alicarin and 100 grams of anthrapurpurin.

Example 8: 10 kilograms of wool, chrome mordanted as usual are stirred at the ordinarytemperature as for acid dyeing, in

liters of a neutral or feebly'acid suspension,

containing 200 grams of flavopurpurin with or without addition otacetate of lime and Turkey-red oil. Thev absorption of the dye is efiec'ted in a few minutes. 4

' Example 9; 10 kilograms of yarn oil-mordanted as usual for. old-red or new-red are cent. alizarin-paste. 1 Example 10: 10 kilogramsof yarn oi mordanted and moistened as in Example 9 are thoroughly kneaded for ten minutes in. the following bath 2%? kilograms of Water,

1400 cubic centimeters of ferrous sulfate so' lution 1:10, 180- grams of crystallized sodium acetate, and 100 grams of a 20 per. cent. alizarin-paste. i

"'Weightabout 20 kilo rams are thoroughly grees Baume, and 100'gr'ams of a 20 per Examplellz (Single-bath process) 10 kilograms of unoiled and unmordanted yarn are Wetted and thewr'ung-out goods"Weigh-- ing about 20 lnilog'rams, "are then thoroughly kneaded for about ten minutes in a bath ofz 27 kilograms of water, 600 grams of crystallized sodium acetate, 1500 cubic centimeters of acetate of lime of 17 degrees-Baum, 1800 cubic centimeters of acetic acid of 6 degrees Baum, 200 grams of 50 per cent. Turkeyred oil F.', 1000 grams of a 20 per cent. aliza rin-paste.

Second operation-{he production of the h H The formation of the lakebegins' to take place already at cold after the action of the alizarin 'dyestufi upon the mordanted fiber.' By the progressive deeper dyeing of the .goods one can very clearly trace the progress of. theformationof the lake; However days are necessary in order to effect the formation of the-lake at ordinary temperature in any way completely. If the goods are not 'oil-mordanted, it'is important after the boilmg and before the production of the lake to dry the goods for some time at to degrees centigrade. Upon warming in the -moist state, the formationIof the lake takes place almost instantaneously, which operation however is. preferably not effected at once afterthe kneading but after allowing tostand for sometime A quarter to half an hour boiling under water suflices to produce the lake. Aistill more permanent lake is formed, if the wrung-outgoods afterthe first operation are steamed undera pressure l'ar manipulation is unnecessary, and the quantityof water has no. influence. On the. other hand its, hardness must be taken into consideration. The-brightening of the dyed goods is effected in the usualway.

' o/ootmiiwxmon or v r AND MORDANT fat - I Yns'r t1rrs. Example 121-10 kilograms of cotton inor- 'danted with alumina ready for'dyeing as usual for Turkey-red are padded atnormal' temperaturewith 50 liters of a; suspension containing 150 grams of algol-yellow with or without-addition of acetate of lime and Turkey-red oil." The f absorption of. the alizarin .as well as of the-algol-yellow is completedin a few minutes. v

- Example 13:10 kilograms of wool chrome mordanted' as usual. are padded. at ordinary temperature in ,60 liters of.a .feebly acidulated suspension containing 200grams 7 process the dimensions of the vats are naturof alizarin and 50 grams of algol-yellow.

1 The. absorption .of the dyestuffs is.i 'com- 65 -plet edin a vfew minutes. f

'- to act upon operation: f I The wrung-out dyed goods are first either warmed under water or 'steam d for the purpose of producing the alizarin lake. .In

order to fix the vat dyestuff, which. is not dissolved either uponsteamingor by boiling of the dyestufifunder wateryit must subsequently be v-atted. The alizarin lake once formed does not' suffer thereby? provided thevatting is done in a careful manner.

After windingfand soaping there are obtained in tints. I v

n. MAGNEsIU LEUoo COMPOUNDS or vA'r nYEsTUrrs.

this way thoroughly fast mixed In dyeing with vatdyestufi's as hitherto practised, the. dyestufi' is always converted-v into the soluble leuco compound usually by means of a reducing agent in presence of strong alkali such as soda-lye,ammonia;or.

lime. lhis applies also for example-in'tiieg case of zinc-lime and ferrous'sulfate-lime insoluble, but the resultin indigo-white is indigo-vats, in which the reducingagent is I converted into the soluble orm by means of calcium hydroxid. As. has been proved by investigations, vat dyestufl's such as indigo :and its derivatives, dyestuffs of the-thioindigo series, and algol-dyes arein thepres -erice of magnesium hydroxid capable of acting evenly upon the .fibers in an aqueous suspension of their magnesium leuco compopnds which are only. slightly soluble" in 4 water. It is. remarkable that 'in'thisv case the more completely than by the useofsoluble other example-of the surprising phenomenon -"absorption of the dyestufl is efiected much that dyestufis insoluble in water are enabled 7 the fibers at ordinary temperature.

.The'advantages of. the imagnensia' vats are manifold; Since magnesium hydroxid has hardly any alkaline reaction, the mag- J fnesla vats are specially suitable for W001 andsilk which as is known do not stand alkali well. .This opens up the possibilityof .dyeing Wool and silk with .vat dyestufi's in -many cases in which the use of vat 'methods has hithertobeen scarcely feasible. Since the combination ,of the magnesium leuco compounds ofthe vat dyestufi'swith the fibersis at first. only loose, the dyestufi can- .be well equalized-by a. slight movement 'or padding'of the goods or by mechanlcal cir- -cu l'ation of the bath; before the more fixed intermediatecoinbinati-on of the 'estuii is brought about. It is also important that for the concentrated baths characterizing the ally small.- A more important point is that air farfmoreslowl yt than soda or lime baths,

which circumstance allows a' more convem' lent and more tractable Working.

1 Example- 14: 200' grams of; algol-yello'w in the form'ofpaste are addedto 50 liters of Water containing 400 grams of magnesium hydroxid "and 600 grains of hydrosulfite. .Aftera short time the formation of the I orangered suspension of the magnesium jleuco compound is completed. kilograms ofcotton are-thenentered; The action of the suspended magnesium -leuco compound proceeds i'n'a short-time and can beaccel'erated by moving or padding the goods or by circu lating the liquor. .The progressive orange dyeing of the goodstogether with the' decoloration of the suspension indicate the progress ofthe operation. After the absorp- .t ion, of the dyestufi iscompleted, the goods are wrung, hung out, Wound, acidulated and f'soaped The evenness andthe' fastness of 1 the dyelng leave nothing to be desired Example. 15: 200 grams of indigo in paste arestirr'ed into liters of Water containing 1400 grams of magnesium hydrox'id and 600 grams. of hydrosulfitefi After a'short time goods. which have '55 the presence of magnesium hy are then added. v

the fiber is completed, the goods are wrung, soaped. It is also the formation of a light green suspension of magneslum' leuco compounds of indigo is completed. 10 kilograms of Wool are entered and treated as in Example 14. The

evenness and fastness of the dyeing are excellent. j

' Example 16: 200 grams of thiomdigo-red in paste are added to 50 liters of Water, con- ,taining 400 grams of magnesium hydroxld Example 17: 1.0 kilograms of cottdn are -padded.'in a suspension consisting of i8 liters of Water and 150 grains of thioindigo j red, fill-grams of algol-yellow and iOO grams ofmagnesium hydroxid until the absorption of thedyestufi is completed. 600 grams of hydrosulfitefdissolved in 10 liters of Water After the reduction upon hung out, acidulatedand possible to proceedby first wringing out the been padded with algolyellow. in .droxid and then introducing them into the ,"necessary quantity of hydrosulfite solution,

becausein the padding not only the dyestuff but-also the magnesium hydroxid is ab sorbedand fixed by the fiber. The dyes "-tu rn;out' even.,and of good fastness.

Z Theieoncentration of the liquors, the proportions of the mixture of magnesium hydroxid, and-hydros'ulfite. and also the temperature may, be :variediwithin wide limits.

dyestuffs combined with with vat dyestuflt's, one may H more Instead of vatting the-vat dyestufi's with hydrosulfite only in the presence of' magneslum hydroxid, it is also possible to proceed. by effecting the vatting with hydrosulfite in an alkaline solution (so.da=or lime) vWith or without addition of magnesium hyd'roxid, after which sufficient quantities of a metal salt such as magnesium chlorid', aluminium 1 sulfate, zinc sulfate, stannous chlorid, stannicchlorid, etc, are added, and the action of the dyestuif from the suspensionof the corresponding insoluble'metal l'euco compound is accomplished. In this Way the alkalinity of the vat may be'reduced as desired, even indeed so faras to be able to work with a vat showing an. acid reaction upon litmus.

In dyeing with; magnesium and other metal leuco' compounds, of-the vat dyestuffs" there may also be employed for the purpose of producing darker tints vat-additions of greater strength, in which case the quan-. titles of dyestuli consumed must be restored for the next operation. In this Way it is possible to produce upon Wool for example, in one operation extremely powerful dyeings ofvery good fastness.

In general feeble dyeings are produced by diluted baths, strong ones by concentrated baths. Apart from the concentration of the bath the temperature during dyeing is also of importance. Cotton absorbs better from cold baths, Wool from Warm ones and silk from tepid ones. It is there-fore practicable in the case of mixed textile fibers to produce any desired effects, by dyeing either all the fibers evenly in tepid baths or only one fiber as preferred.

Further experiments have shown that animal fibers (wool or silk) may be caused to absorb vat dyestuffs in a (plantitative manner from quite diluted baths, if the reaction is assisted by Warming. In this Way .vat dyestuffs maybe fixed simultaneously, which otherwise could only with diliiculty be dyed in the vat beside one another on account of their varying ailinity for vat dyestuffs. New effects n'iay-be obtained by; dyeing Vat acid or mordant dyestuffs in one bath. Also in this case q'uite definite proportions of quantities of the components may be determined from the foregoing. v

proceed further in order to convert the'unstable compound into thedyeing proper, as. has been done above in the second operation. In combined dyeings by vat dyestufi's with mordant dye- .stufl's,'the goods are subsequently submitted to vetting, then hung out,'wound and soaped. The vat dyestufl combined in an unstable" condition with-the fiber is thereupon'con- 'verted into the stable compound proper.

The metal lakes of the-mordant dyestufi's already formed upon the fibrous material If one has to deal exclusively described.

remain unaffected by alkaline vats provided their alkalinity, concentration and temperature do not exceed certain lmnts. After vatting the goods are hung out, WOllIlCl and.

soaped.

Example 18: 200 grains grams of algol-yellow are suspended in 200 liters of water; the liquid is acidulated with acetic acid and 10 kilograms of moistened Woolen yarn are entered. The temperature is graduallyraised to 60 degrees centigrade,

with frequent movement of the goods. After the goods have been allowed to cool, the quantity of dyestufi" taken up 'is'fixed" upon the fiber in a feebly alkalinehydrosulfite solution or in a magnesium hydroxidhy'drosulfit'e vat. Afterward the goods are hung out, wound and soa'ped.

Example 19: One proceeds as given in Example 18, but in place of Woolen yarn the same quantity of Ghappe-silk is used.

Example -20: 200 grams of indigo and 200 grams of thioindigo-red to 10' kilograms of woolen yarn, Dyeing-is efiectcdas in Ex ample 18.

Example 21: Dyed as Example 20, but

insteadof. woolen yarn, the same quantity of Chappe-silkis treated.

Example 22: 200 grams of alizarin' and 200 grams of. indigo; 10 kilograms of silk scribed j'Example 1 8.

Example 23": 200 grams .of alizarin and 200 grams of indigo; IO-kilograms of chrome prepared for Turkey-redarcdyed as premordanted 'woolen yarn are dyed as stated in -Exan 1p1e 18.

, Example 24; 200' grams of quinoline-yeL' low and 200gran1s of indigo; 10 kilograms Chappe-silk'are as in Example 1.8

, Example 25: 200 15 of algolryellovr',

10 kilograms of Woolen yarn-are treated as in Exanjiple18."" Y

The term dyeing compounds used in the'above, d'escri tion andin thelclaims-cova 'er-s vat dye-stu s,-leuco-metal salts of the' vat dye-stuffs and mordant dye-stuffs of the alizai in series.

Having thus'.described inventionytvhat I claim as new and desireto secure by etters Patent is p l. A process for dyeing with dyeing compounds insoluble in Water, said process comprising bringing the goods'to be dYGCl lDtO of indigo and 200 stable dyeings proper.

contact with an aqueous suspension of dyeing compounds insoluble in Water and free from sulfur and thickening; and then converting the resulting unstable dyestufi coinpounds into stable dyeings proper.

2. A process for dyeing with dyeing compounds insolub'ie in Water, said process com-- prising bringing the goods to be dyedinto contact with an aqueous suspension of dyeing compounds insoluble in water and free from sulfur; and then converting the resuiting unstable dyestuff compounds into 3.- A process for dyeing with dyeing com pounds insoluble in water, said process'comprising bringing the goods to be dyed into contact with an aqueous suspension of'dyceing compounds. insoluble in water and free from thickening; and then converting the resulting unstable dyestufi compounds into stable dyeings proper.

f 4 A process for, dyeing with vat dye- :stufi's insoluble infi'vater comprising first bringing the" goods into contact 'ivith' anaqueous suspension of the dyeing compounds inselnble in Water, then convertingthe resulting unstable tdyestuff compounds into stable dyeings, proper by subsequent vat-' ,ting upon the fiberand oxidizing the leuco compounds formed.

A process for dyeing with dyeing C011]:

pounds insoluble in water, said processcomprising bringing the goods to be dyed into contact with ajcold concentrated aqueous suspension of dyeing compounds insolublein' water and free fromthickeni'n and then 0 e converting the resulting unstable dyestufi compounds into stable dyeing-s proper. r

6. Aproces's for dyeing withxeat dyestuffs insoluble inrra'ter comprising first bringing goods into contact ,Wlllil an aqueous suspension of the dyeing compounds insoluble in Water, and then cor uverting the resulting unstable dyestufi' compounds into stable dyeings proper by subsequent vattingupon the 

